Optimization of Manganese Coupling Reaction for Kilogram-Scale Preparation of Two Aryl-1,3-dione Building Blocks
| Autor: | Vijayagopal Gopalsamuthiram, Krishna Sawant, Srinivas Subramanian, Nigel James Willetts, George Robert Hodges, Matthew Brian Hotson, Sujit K. Ghorai, Anne-Marie Hogan, James Nicholas Scutt, Louisa Whalley, Dinesh Pagar, Tomas Smejkal, Jonathan Dallimore, Anup M. Jawalekar |
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| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Aryl Organic Chemistry chemistry.chemical_element Epoxide Manganese 010402 general chemistry 01 natural sciences Coupling reaction 0104 chemical sciences Catalysis chemistry.chemical_compound chemistry Reagent Organic chemistry Lithium Physical and Theoretical Chemistry Alkyl |
| Zdroj: | Organic Process Research & Development. 21:1625-1632 |
| ISSN: | 1520-586X 1083-6160 |
| DOI: | 10.1021/acs.oprd.7b00241 |
| Popis: | Aryl-1,3-diones represent a promising new class of herbicidal acetyl-CoA carboxylase (ACCase) inhibitors. The original synthesis of this structural motif employed in the research phase involved a selenium oxide mediated oxidation, the use of diazoacetate and aryl lead reagents, and a low temperature oxidation of an aryl lithium intermediate, so it was not well suited to large scale synthesis. For kilogram scale synthesis of the two aryl-1,3-dione building blocks (3 and 4), we developed an alternative route which employs a manganese or manganese–copper catalyzed alkyl Grignard coupling and a semi-pinacol rearrangement of an epoxide as the key steps. The optimized conditions could be of general interest as scalable methods for the synthesis of 2-alkyl substituted benzaldehydes and of 2-aryl-1,3-diones. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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